In this paper, we report on the development of a bench-stable borane for frustrated Lewis pair catalyzed reduction of aldehydes, ketones and enones. The deliberate for finetuning of structural and electronic parameters of Lewis acid component and the choice of Lewis base provided for the first time, a moisture tolerant FLP catalyst. Related NMR and DFT studies underpinned the unique behavior of this FLP catalyst and gave insight into the catalytic activity of the resulting FLP catalyst.

The first halonium‐ion‐based helices were designed and synthesized using oligo‐aryl/pyridylene‐ethynylene backbones that fold around reactive iodonium ions. Halogen bonding interactions stabilize the iodonium ions within the helices. Remarkably, the distance between two iodonium ions within a helix is shorter than the sum of their van der Waals radii. The helical conformations were characterized by X‐ray crystallography in the solid state, by NMR spectroscopy in solution and corroborated by DFT calculations. The helical complexes possess potential synthetic utility, as demonstrated by their ability to induce iodocyclization of 4‐penten‐1‐ol.